An inorganic–organic hybrid material with a novel oxometallic framework: Hydrothermal synthesis and characterization of [Zn3O3(C13H14N2)3]V6O15

Abstract

a b s t r a c tA new hybrid material [Zn 3 O 3 (C 13 H 14 N 2 ) 3 ]V 6 O 15 (1) with extended framework structure has been synthesized hydrothermally and characterized by vibrational spectroscopy, thermogravimetry and complete single crystal X-ray diffraction analysis. The compound has a complex three-dimensional covalent framework structure. It exhibits a fully oxidized novel oxometallic framework containing 10-membered {V 4 ZnO 5 } oxometalate rings and 4,4 0 -trimethylene dipyridine ligands (C 13 H 14 N 2 ) that connect pairs of crystallographically equivalent zinc atoms. The extended structure of 1 may also be viewed as containing a framework of corner-sharing {VO 4 } and {ZnO 2 N 2 } polyhedra together with 4,4'-trimethylene dipyridine ligands linking zinc centers. The hybrid material is thermally stable up to 323°C. It contains metal centers and coordination geometry that make it a potentially attractive model compound for investigating the structures of metallo-organic biomolecules by use of solid state NMR spectroscopic techniques. Design and synthesis of functional materials has attracted considerable attention in recent years [1]. This has led to a new class of inorganic-organic hybrid materials with rich topological diversity and potential applications in catalysis, gas storage, sorption and photochemistry [2][3][4][5]. Hybrid materials have shown excellent laser efficiencies and photostabilities [6], fast photochromic responses [7], as well as high and stable optical responses [8]. These materials can also be used as pH sensors [9] and many of them have shown attractive gas storage capacity [10][11][12][13][14].We have been interested in the design and synthesis of inorganic-organic hybrid framework materials by combining metalorganic moieties and oxometalate motifs. We have successfully employed synthetic strategies using metal-organic complexes as linkers to cross-link vanadium oxide chains and layers to generate a series of open-framework hybrids and neutral networks. The metal-organic complex also provides the charge balance required to generate a neutral framework [15][16][17][18][19][20][21]. In this approach the organic components act as ligands to secondary transition metal centers giving rise to bimetallic, organically templated hybrid materials. Here we report a new hybrid material containing a novel oxometallic framework [Zn 3 O 3 (C 13 H 14 N 2 ) 3 ]V 6 O 15 (1) which was prepared hydrothermally and characterized by FT-IR, elemental analysis, manganometric titration, thermogravimetric analysis and complete single crystal X-ray diffraction analysis.A mixture of NH 4 VO 3 (1 mmol), 4,4 0 -tmdp (1 mmol), ZnSO 4 Á 7H 2 O (0.5 mmol), C 2 H 5 OH (85.76 mmol, 5 ml), H 2 O (555.5 mmol, 10 ml) was placed in a 23 ml teflon-lined Parr reaction vessel and stirred continuously for 10 min. The reaction mixture (pH = 5.1) was then treated hydrothermally at 125°C for 5 days. The reaction was then cooled to room temperature for 24 h and colorless crystals of 1, which were covered with a black shiny impuri...

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“…During the course of our ongoing work on the design and synthesis of new types of vanadium oxide based materials, − we have isolated a mixed-valence species, MgV V 2 V IV 2 O 10 ·4H 2 O ( 1 ). To our knowledge, 1 is the first example of a model compound for the mineral melanovanadite.…”

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“…In this approach, hybrid materials containing neutral framework structures are generated by combining anionic oxovanadate building units with metal-organic cationic complexes. Our effort has led to the synthesis and characterization of a variety of novel materials [27][28][29][30][31][32][33][34][35][36].…”